Color couplers containing long chain alkylaminoisophthalicester groups



United States Patent C COLOR COUPLERS CONTAINING LONG CALKYLAMINOISOPHTHALICESTER GROUPS Robert F. Coles, North St. Paul,Minn., and Heinz Schulze, Cincinnati, Ohio, assignors to General Aniline& Film Corporation, New York, N.Y., a corporation of Delaware NoDrawing. Filed Oct. 31, 1957, Ser. No. 693,509

9Claims. (Cl. 96-55) This invention relates to color photography andparticularly to color-forming compounds.

The use in color photography of color-forming compounds, which reactwith the oxidation or development product of primary aromatic aminodeveloping agents to form colored images upon photographic development,is well-known. The colored compound thus formed is deposited next to thesilver grains of the silver image during development. The couplercompounds as employed above may be added to the color developersolutions or they may be incorporated in the gelatino silver-halideemulsion.

When used in photographic emulsions, the couplers may be dissolveddirectly in the gelatin or other hydrophilic colloid. In such case, thecouplers must have groups rendering them alkali soluble such ascarboxylic acid or sulfonic acid groups.

Alternately, the couplers may be incorporated in a photographic emulsionby dissolving them in a waterimmiscible or oily organic solvent anddispersing the resulting solutions in the photographic emulsion.

In the manufacture of emulsions containing couplers,

considerable difficulty is encountered in obtaining couplers of highpurity, particularly couplers containing carboxylic or sulfonic acidgroups. In the case of couplers that are added to emulsions in the formof dispersions, problems are experienced in obtaining couplers ofsufficient solubility in organic solvents. Similarly, many couplers havea tendency to diffuse in the medium in which they are incorporated.Finally, many of the couplers mentioned in the prior art give rise tocolored photographic images of undesirable spectral characteristics.

It is, therefore, an object of the present invention to provide colorformers which can be readily purified by recrystallization.

A further object is to provide color formers which containing thefunctional or reactive group which reacts with the oxidation products ofthe primary amino aromatic developing agents to yield color images, saidreactive groups comprising a reactive methylene group, such asketomethylene, i.e., COCH CO;

--CO-CH CN- C 0CHif]J N etc., or a reactive phenolic hydroxyl group,e.g.,

CIJH C=C e.g., phenols and naphthols, which are reactive in the ortho orpara position relative to the hydroxyl group; X represents a CO- or SOgroup; Z represents hydrogen, halogen, e.g., chlorine, bromine andiodine, an

H 1 it i Q --ONOO @omom alkyl group, e.g., methyl, ethyl, n-propyl,n-butyl, isobutyl, n-amyl, n-hexyl, etc., an aryl group, e.g., phenyl,halophenyl, e.g., chlorophenyl, bromophenyl, etc., naphthyl, etc., analkoxyl group, e.g., methoxy, ethoxy, npropoxy, n-butoxy, etc.; R and Rare short chain alkyl groups such as methyl or ethyl and Alk is an alkylgroup of at least 10 carbon atom, i.e., decyl, dodecyl, tetradecyl,octadecyl, etc.

The following compounds illustrate the isophthalic esters which may beused according to our invention.

I COiCH soluble salts, i.e., sodium, potassium, ammonium, etc.

can be incorporated in gelatin emulsions either directly or bydispersing a solution of the coupler in organic solvents.

A still further object is to provide color couplers which are fast todiffusion in the emulsion.

Other objects will appear herein as the description A-CONH X-III-Alkwherein A represents that part of the coupler molecule CO2CH3 and thecorresponding dicarboxylic acid and its watersoluble salts, i.e.,sodium, potassium, ammonium, etc.

( C OsOHa I n n SOr-N OOzCHa and the corresponding dicarboxylic acid andits watersoluble salts, i.e., sodium, potassium, ammonium, etc.

CO2CHa and the corresponding dicarboxylic acid and its watersolublesalts, i.e., sodium, potassium, ammonium, etc.

OCH:

and the corresponding dicarboxylic acid and its watersoluble salts,i.e., sodium, potassium, ammonium, etc.

Cl COICHa and the corresponding dicarboxylic acid and its watersolublesalts, i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts,i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts,i.e., sodium, potassium, ammonium, etc.

ll 1 o-N- C ieHa-l COzCHa and the corresponding dicarboxylic acid andits watersoluble salts, i.e., sodium, potassium, ammonium, etc.

H GIEHM and the corresponding dicarboxylic acid and its watersolublesalts, i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts,i.e., sodium, potassium, ammonium, etc.

a? l r OOHz-ON OCH:

CrsHa1 SOs-N? GOQOHE C OnCHa and the corresnondmg dicarboxylic acid andits watersoluble salts, i.e., sodium, potassium, ammonium, etc.

O E I II I Q I C1s a1 O-- -CO1CHa n 0 and the corresponding dicarboxylicacid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

ll OH ll l SOz-N COQCH! and the corresponding dicarboxylic acid and itswatersoluble salts, i.e., sodium, potassium, ammonium, etc.

(15) OH CH3 0 H. n C' -N COaOHs and the. corresponding dicarboxylic acidand its watersoluble salts, i.e., sodium, potassium, ammonium, etc. Thecompounds hereof are prepared by condensing a 5-alkylaminoisophthalatewith an acid chloride or sulfonlychloride of the following generalformulae:

NO S0201 with Z representing the same groups as above. The condensationsare advantageously carried out in an inert solvent like benzene orxylene at elevated temperatures so that the hydrogen chloride formedduring the reaction is discharged immediately. After reduction of thenitro group, the resulting amine is condensed with a carboxylic acidderivative of the color-forming residue by known methods. Naturally, theesters can be hydrolyzed and their carboxylic acids used as colorformers in the same Way as used herein. The above compounds may be usedin the form of their esters or their acids. If the esters are employed,they are dissolved in a suitable solvent such as a mixture of 50 partsphenethyl alcohol, 40 parts of tricresyl phosphate and 10 parts ofn-butyl phthalate and the resulting solution incorporated in theemulsion as a fine dispersion. If the acids are employed, they are 5introduced into the emulsion directly as an alkali metal salt such asthe sodium salt.

I Example 1 Compound (1) is prepared as follows: Dlmethyl5-(3-nltro-N-octadecylbenzamtdo)tsophthalate C O O OH: (lliaHw Q II IN02 COUCH-a Dlmethyl B-amtno-N-octadecylbenzamido) tsophthalate C 0 OCH:

NH COOCHa 80 grams of the foregoing product was hydrogenated withplatinum oxide in 100 ml. oflmethanol at 50 C. More methanol was addedand the'solution filtered hot from the catalyst and a small quantity ofan insoluble white residue. The solvent was evaporated on a steam bathin vacuum. Yield 66 g. of a slightly brownish viscous oil.

Analysis: Calc.72.40% 72.22% C, 9.17% H.

C, 8.96% H. Found- 1-h drox -3-[N-(35-dlcarbomethoxyphenyl)-N-(octadecyl) y y carbamyH-Z-naphthamHde COOCHI(EOOCH:

- 18.3 grams (0.03 mole) of the foregoing product and 9 g. (0.033 mole)of phenyl 1-hydroxy-2-naphthoate.

Example II Compound (2) was prepared in the same way as Compound (1)while substituting the isomeric p-nitrobenzoy-l chloride for them-nitrobenzoyl chloride.

1- Compound (2) melted at 139-140 C.

zenesulfonyl chloride.

Example III I Compound (3) was prepared as follows:

Dlmethyl S-p-nltro-N-octadecylphenylsulfonamidolsophthslate C O O CH:CraHn Dirnethyl 5-0ctadecylaminoisophthalate was condensed with4-nitrobenzenesulfonyl chloride in' 'refluxing xylene according toExample I. The condensation product melted at 9191.5 C.

Dimethyl 5-pamino-N-octadecglphenylsultonamldolsop a e OOCHs hthal c o 00H- (liisHu HiN-SO2N I c o 0 cm The nitro compound was reduced to thecorresponding amine using platinum oxide as catalyst; M.P. 91-915 C.

N (3,5-dlcarbomethoxyphenyl)-N'-ootadecy1-N- (l-hydroxy-2-naphthy1)su1fanilam1de C 0 O CH CiaHu OOCHI Example IV Dlmethyl5-(4-chlore3-n1tropl1enyl-N-octadecylsultonamtdo) tsophthalate C O O CH:(IJ1aHa1 Ol-Q-SOa-N N02 60 O CH:

In a 1 liter 3-necked flask, equipped with a reflux condenser andstirrer was placed a solution of 92.4 g. (0.2 mole) ofoctadecylaminoisophthalic acid dimethyl ester in 500 ml. of dry toluene.5 drops of pyridine was added followed -by 51.2 g. (0.2. mole) of4echloro-3-nitroben- Thesolution was refluxed for 18 hours and thesolvent then removed at reduced pressure. The4-ch-loro-3-nitrobenzenesulfonyl chloride used above was prepared fromthe potassium salt of the con-responding acid using phosphorouspentachloride as the chlorinating agent and phosphorous oxychloride as asolvent. The residual oil was crystallized from about 1200 ml. ofpetroleum ether; B.P. -100 C. The resulting product was digested with 1liter of boiling methanol, cooled and filtered. Yield g., M.P. 93-94 C.

Dlmethyl 5- (3-amluo-4-chloropl1enyg-N-oetadecylsultonsmtdo) e A mixtureof 30 g. (0.044 mole) of the above nitro compound and 200 ml. ofmethanol were reduced in a low pressure heated hydrogenator with Raneynickel The condensation product weaver Dtmethyl 6-(3u-benzoylacetamIdmkchIorophenyl-N-octadecylsulfonamldo)isophthalate.

c 0 on: l iaHn Qantas- 3:

' doc cm.

In a 1" liter-3mecked flask, equipped with a stirrer, vertical steamjacketed condenser and dropping funnel, was placed a solution of. theabove amine (48 g., 0.074 mole) in 500 ml. oi. dry'xylene. The solutionwas treated dropwise at reflux with etyl-benzoylacetate (17.3 g., 0.09mole), and the resulting solution was refluxed for 8 hours. Afterremoval of the solvent; on a steam bath at reduced pressure, theresidual oil was dissolved in 800 ml. of methanol, treated with charcoaland filtered. The filtrate was decanted from a small amount of dark oil,treated again with charcoal and filtered. The filtrate was cooled, theproduct collected and washed with cold methanol. Yield 25 g-,, M.P.107-108 C.

Example. V Compound (9) was' 'prepared by condensing dimethyl" (3-amino4"-chlorophenyl N- octadecylsulfonamidof 3 Compound 10) was I preparedas: follows-2 Dimethyl 6*- (3 nttrophenyl N-octadecylsultonamtdo) lso= Iphthalate' COOiCHa'. 13 31.

l N01 C O 0 CH3 In lei-500ml. 3'-necked flask, equipped with astirrerand a reflux condenser, were placed 200 ml. of dry xylene,and.46.2-. g...(-.( ).Ol mole) of, 3-octadeoylaminoisophthalic aciddimethyl; ester: 3-nitrobenzenesulfonyl chloride (22.21g.-,,0.l+ mole)was added and the solution heated at gentle reflux. for 18 hours.,Thes'olvent was removed from the dark solutionatreduced pressure andthe residue triturated' with methanol (l50=ml.). After coolingthe-solution, the solid was collected-by filtration andiwashed withmethanol. The product was dissolved in 200' ml. of' petroleum ether;B.P. 90-l00 C. The. solutionwas treated withv charcoal and filtered.The:

filtrate was diluted with an equal volume of petroleum etliefyFiPEU-GO'Alter cooling, theswhitef cnystal line solid was collected by filtrationand waswashed with petroleum ether. The product was recrystallized from400 ml. methanol; M.P. 74-75 6.

Dtmeth'yr 5-(e amtnophenyl moctadecylsulfonamidoltam phthalate v oooon.OraHn NH: O 0 CHI Amixture-of' Z7.7-'g., (0.043 mole) of theabovenitrocompound in 200'. ml. of methanol were reduced'in" a low pressurehydrogenator with platinum oxide catalyst.

The white crystalline solid obtained. was dissolved in 50 m1. of hotpetroleum'ether; B.P. 30-60 C. The solution was cooled inice-and thecrystalline solid which separated. was collected' by filtration anddried. Yield" 21 g., M.P. 76-78 C.

l-hydrox -8-[N- 8,5-dicarbomcthox hen 1)-N-(octadec l) y tiulta'myllQnaphthiiQiMdiL' y CO 0 CH;

A mixture of the amine' prepared as above (4.5 g., 0.017 mole)wasxheated at reduced pressure (5-10 mm.) on a metal bathfirst-at-140--l50 C. for A hour and then at 160-l70 C. for hour.Methanol (100 ml.) was added to the hot melt. After tri-turating' for ashort time, the oil crystallized. The warm mixture wasfiltered and T thesolid was crystallized from petroleum .ether; B.P.

C. Yield 7.8 g., M.P. l l4ll5 C.

Analysis: Calc.--68.70% C, 7.38% 68.74% C, 7.39% H.

Example VII Compound (11) was prepared by condensing dimethyl 5-(3aminophenyl-N-octadeeylsulfonamido) isophthalate (10 g., 0.016 mole)with ethyl benzoylacetate (3.8 g., 0.02 mole) in 100 ml. of dry xylene,following the procedure used to prepare Compound (8).

The" amine was the same used for the preparation of Compound (10).

H. Found A solution of 1.5 'g. of Compound (5) wasdissolved in 6.0 g. ofa mixture consisting of 50 parts phenethylalcohol, 40' parts oftricresyl phosphate "and 10 parts of n butyl phthalate-and the resultingsolution dispersed'iin' 20ml. of a 6% gelatin solution containing 0.05of" Einulsification was efiected by high-speed.

lauryl' sulfate; I agitation in a small' Waring Blendor. The" abovedispersion of coupler was mixed. with..50 g. of a melted silverhalidegelatin emulsion andthen coated on a suitable support, set and 'dried intheusual manner. On exposure aIIdfd'CVGlOPIILBHlZEOfTfl'fi emulsionwitha developingsolir tion employing Z-aminoeidiethylaminotoluene as thede I veloping agent and'subsequent removal of-' silven'a yellow 75'image was obtained.

Compound was treated with alcoholic KOH to convert the di-ester into thecorresponding potassium salt. The salt was dissolved in alkali andmethanol and added to a silver-halide emulsion according to theprocedure of U.S. Patent 2,186,849.

Various photographic developing agents can be employed with the couplersof our invention. The primary aromatic amino developing agents aregenerally suitable including the phenylenediamines and aminophenols.Suitable compounds are 4-aminoaniline, 4-ethylaminoaniline,4-dialkylaminoaniline, e.g., 4-dimethylaminoaniline,4-diethylaminoaniline, 4-[N-(p-hydroxyethyD-N- ethyl] aminoaniline, 4amino N-ethyl-N-(fi-methanesulfonamidoethyl)-2-methylaniline sulfate,and the like. The above developing agents are preferably used in theform of their salts such as the hydrochloride or hydro sulfate as theyare more soluble and stable than the free bases. All of these compoundshave a primary amino group which enables the oxidation product of thedeveloper to couple with the color compounds to form dye images. Afterremoval of the silver image by bleaching and fixing in a mannerwell-known to the art, the color image remains in the emulsion.

A suitable developing solution can be prepared as follows:

G. 2-amino-5-diethylaminotoluene 2 Sodium carbonate (anhydrous) 20Sodium sulfite (anhydrous) 2 Potassium bromide 0.2

Water to make 1 liter.

The exposed silver-halide emulsions containing the color formers aredeveloped in the above solution in the usual manner.

It will be understood that the examples and modifications set forthherein are illustrative only and our invention is to be taken as limitedonly by the scope of the appended claims.

We claim:

1. A silver-halide emulsion containing a coupler compound of thefollowing general formula:

Z A-CONH ROOC COOR wherein A is an organic color forming residue of thetype capable of color coupling with the oxidation products of a primaryaromatic amino silver halide developing agent, said color formingresidue having a grouping selected from the class consisting of al-hydroxy-Z-phenyl group, 1-hydroxy-2-naphthyl group and abenzoylmethylene group; X is selected from the class consisting of CO--and --SO Z is selected from the class consisting of hydrogen, halogen,lower alkyl, lower alkoxyl and an arcmatic hydrocarbon radical of thebenzene and naphthalene series; R and R are selected from the classconsisting of hydrogen, lower alkyl, an alkali metal, ammonium and Alkis an alkyl group of from to 18 carbon atoms.

2. The article as defined in claim 1 wherein the organic color formingresidue A is a l-hydroxy-Z-phenyl group.

3. The article as defined in claim 1 wherein the organic color formingresidue A is a benzoylmethylene group.

4. The article as defined in claim 1 wherein the organic color formingresidue is a l-hydroxy-Z-naphthyl group.

COOCH;

6. A silver-halide emulsion containing a coupling compound of thefollowing formula.

C O O CH: C") (ilisHu C-N O OCH:

1 N-H (i=0 7. The method of producing a colored photographic image in asilver-halide emulsion layer which comprises exposing the layer anddeveloping said layer with a primary aromatic amino developing agent inthe presence of a coupler compound of the following formula:

Z A-CONH ROOC COOR' wherein A is an organic color forming residue of thetype capable of color coupling with the oxidation products of a primaryaromatic amino silver halide developing agent, said color formingresidue having a grouping selected from the class consisting of al-hydroxy-Z-phenyl group, l-hydroxy-Z-naphthyl group and abenzoylmethylene group; X is selected from the class consisting of CO-and -SO Z is selected from the class consisting of hydrogen, halogen,lower alkyl, lower alkoxyl and an aromatic hydrocarbon radical of thebenzene and naphthalene series; R 'and R are selected from the classconsisting of hydrogen, lower alkyl, an alkali metal, ammonium and Alkis analkyl group of from 10 to =18 carbon atoms.

8. A photographic emulsion for forming colored images comprising agelatino silver-halide emulsion having incorporated therein a couplingcompound of the following formula:

C O O CH! 0 raHn SOs-N- 9. A photographic emulsion for forming coloredimages comprising a gelatino silver-halide emulsion hav- 1'1? 7' 12 Mgincorporated 'therein-a' coupliiagcompound o'f the fdl-RfrencesrCite-drin thezfile'of this patent lowmg formula UNITED STATESPATENTS 0 018B" fi 2,186,849 Wilmanns et a1 Jan. 9, 19,40 n 1, 2,498,466Thompson Feb. 21, 19 50: 7 2,652,329 McCrossen et a1 Sept. 15, 19532,657,134 Graham et a1. Oct. 27, 1953. OOOH:

1. A SILVER-HALIDE EMULSION CONTAINING A COUPLER COMPOUND OF THEFOLLOWING GENERAL FORMULA: